Sulfo-esters of alcohols bearing a hydrophilic substituent



' member of the group consisting of the United States Victor Mark,Evanston, 111.,

Products Company, Delaware assignor to Universal Oil Des Plaines, Ill.,a corporation of No Drawing. Application December 30, 1953 Serial No.401,431

6 Claims. (Cl. 260-456) This application relates to compositions ofmatter herein characterized as sulfo-esters and to a process for thepreparation of said esters. Some of the specific applications of theinventionconcern certain types of sulfoesters which have surfaceactivity in aqueous or anhydrous solvents, said esters being theproducts formed by esterifying a hydrocarbon sulfonic acid with anhydroxysubstituted organic compound having an additional hydrophilicsubstituent which balances the effect of the hydrophobic hydrocarbongroup in an appropriate solvent therefor such as water, hydrocarbon andester-oils, alcohols,

etc.

In one of its embodiments the present invention relates to a hydrocarbonsulfonic acid ester of an alcohol bearing a hydrophilic substituent.

Another embodiment of the invention is directed to a process for thepreparation of a hydrophilically substituted sulfo-ester compound whichcomprises condensing a mono-hydrocarbon substituted sulfonyl derivativewith a compound bearing a hydrophilic substituent and containing a groupcondensable with said sulfonyl derivative to yield said sulfo-ester.

A more specific embodiment of the invention relates to a process for thepreparation of a surface active compound which comprises condensing amono-hydrocarbon substituted sulfonyl derivative with a hydrophilicallysubstituted hydroxy compound condensable with said sulfonyl derivativeand selected from the group consisting of an alcohol and a phenol, thehydrocarbon substituent of said sulfonyl derivative containing at least8 carbon atoms when alkyl and at least 11 carbon atoms when a monoanddicyclic cycloalkyl, aryl, aralkyl, alkylaryl, hydroaryl, hydro-.arallryl and hydroalkylaryl radicals.

The compounds of this invention are utiized primarily, although notnecessarily, tain members of the series being emulsifying agents, whileothers are highly effective detergent and wetting agents. Depending uponthe molecular structure and also upon whether the hydrophilic grouppresent in these compounds has an active, water-solubilizing effect onthe compound as a whole, individual members of the series may be solublein water or alternatively may be preferentially soluble in organicsolvents such as alcohols, liquid hydrocarbons, etc. Thus, certainmembers of the present series of products may have a highly eflectiveWater solubilizing group in their molecular structure and may beutilized for detergent purposes in aqueous systems, such as forlaundering. Other individual members of the present series of compoundsmay have a relatively more active hydrophobic group in their molecularstructure and may be more effective as surface active agents innon-aqueous solvents, such as lubricating oils, etc. In general, theclassification into which any particular compound may fall is dependentupon the number, size and specific character of the respectivehydrophilic and hydrophobic portions of the molecule.

as surface active agents, ceratent O The compositions of the presentinvention, including the products useful as surface active agents, arecharacterized essentially as alcohol or phenol derivatives ofhydrocarbon sulfonic acids in which the portion of the ester moleculeconsidered as being derived from the alcohol or phenol bears at leastone hydrophilic substituent. These compounds, which are essentiallysulfo-esters, in general have the following structure: R-SO -O-R'Xwherein R represents a hydrocarbon group, R a polyvalent organicradical, being the organic residue attached to an hydroxyl group of theoriginal alcohol, phenol or ester reactant utilized in the preparationof the present sulfo-esters, and X represents a hydrophilic substituentor a radical which possesses the property of increasing thewater-solubility of the composition as a whole. The members of the aboveseries of compounds which have surface active properties in aqueous ornon-aqueous solvents are selected from the sulfo-esters in which thehydrocarbon group, R, of the composition is selected from alkyl groupscontaining at least 8 carbon atoms per group and from cycloalkyl, aryl,aralkyl, alkylaryl, hydroaryl, hydroaralkyl, and hydroalkylaryl,containing at least 11 carbon atoms per hydrocarbon substituent, thelatter bydrocarbon groups providing the requisite hydrophobic portion ofthe resultant composition which is essential to the development ofsurface activity or detergency in the final product. In the productionof the present sulfoester type compositions which have surface activity,the following Table 1 presents a number of suitable hydrophobichydrocarbon groups and their structural configuration which may beutilized in the preparation of the surface active members of the presentcompositions:

TABLE I Typical hydrophobic-hydrocarbon substituents in surface activesulfa-esters Alkyl:

n 2n+l n: 8-30 Aryl, mononuclear:

Cm 2m+l Patented Apr. 15, 1958 Hydroaryl, hydroalkylaryl andhydroaralkyl: Partial and complete hydrogenation products of the abovearyls and aralkyls.

TABLE 11 Typical alcohol and polyol derivatives containing hydr0- philicgroups utilizable in forming surface active sulfaesters Alkanolsulfonates:

HOC H- SO M n: 1-10 M=electropositive, salt-forming metal or ammoniumradical Polyol sulfates:

Hoc,,H o-so M),

y=1-16mt does not exceed n M=hydrogen or an electropositive salt-formingmetal or ammonlum radical Mono-hydroxycyclo-alkyl sulfates:

HO-C Ha a- 0-3 03M) y M=hydrogen or an electropositlve metal or ammoniumradical Hydroxyaromatic sulfonates:

(0 n InH) v (OHVGSWM =hydrogen or an electropositive metal or ammoniumradical Aralkylol sulfonates:

H0 (kHz-Q SOzM M=hydrogen or an eiectropositive metal or ammoniumradical Hydroxy acids M=hydrogen or an electropositive metal or ammoniumradical 75 Aromatic:

(H0)=-Ar( (Ga flml'l) I Ar=monoor dicyclic aryl or hydroaryl M =hydrogenor an electropositive metal or ammonium radical Monoand polyalkanolamines:

n=2 or 3 (0:1, 2, 3 aHydroxy-polyoxyalkylene-w-(N-polyalkanol)-arnmonium sulfate:

n=2 or 3 0:1, 2, 3 The products of the present invention, referred toherein as sulfo-esters, contain a hydrocarbon group of the typeillustrated in Table I, above, a sulfonyl group (SO substituted on thehydrocarbon portion of the molecule and an oxy-substituted organicradical bearing a hydrophilic substituent (-ORX) joined to the othervalence bond of the sulfono group through the oxy-linkage. Thus,compounds within the scope of the present invention have the followinggeneral structural formula:

wherein R is a hydrocarbon group containing at least 8 carbon atoms, SOis the sulfonyl group, R is a polyvalent organic radical, X is ahydrophilic substituent on the organic portion of the compound and thecombination of OR-- and X= represents a hydrophilically substitutedorganic radical derived from a monoor a polyhydric alcohol or phenol. Inone of the specific embodiments of this invention wherein a surfaceactive agent is a desired end product of the present process, thehydrocarbon group, R, of the above structure is a radical havinghydrophobic properties, such as an alkyl group containing at least 8carbon atoms per group, a cyclic hydrocarbon radical or a monoordicyclic aryl, cycloalkyl, alkylaryl, aralkyl or a partialy orcompletely hydrogenated aryl, alkylaryl, or aralkyl containing at least11 carbon atoms per group and having the structure hereinaboveillustrated and provided in Table II. Another specific embodiment ofthis invention concerns detergent products and the process for theirpreparation, in which compounds, the eifect of the hydrophilicsubstitutent substantially balances the eifect of the hydrophobichydrocarbon substituent in a solution of the resulting compound, theproducts having detersive qualities comprising a special class ofsurface active agents which not only reduce the surface tension ofsolvents such as water and organic liquids, but also have the additionalqualities essential for detergency and are thereby capable of cleaningsoiled articles washed in a solution of the product. This invention isparticularly directed to the production of those compounds havingdetergency in a suitable solvent therefor and their chemicalconfiguration may contain one or more hydrophilic substituents permolecule, as required, to provide a composition in which the hydrophiliceffect of the group is suflicient to substantially counterbalance theeffect of the hydrophobic hydrocarbon group in solution. The number ofsuch hydrophilic substituents required for detergency is generally notgreater than one substituent per molecule, although as many as 4 may bepresent in the structure of the compound to prO- vide the desired degreeof surface activity.

Typical compounds which have detersive properties Where it is a wholenumber having a value of from 1 to about 25, representing an average fora mixture of compounds. Compounds of this structure may be prepared bysulfonating With fuming sulfuric acid, oleum or sulfur trioxide adodecane, preferably n+dodecane, to form the corresponding dodecylsulfonic acid and tl'iereafter reacting, at esterifying reactionconditions, the sulfonic acid with a polyethylene glycol (anm-hYdIOXYethYl-whydroxyethoxy-poly-oxyethylene) The product may also beprepared from the sulfonyl chloride, which in turn may be made by thechlorosulfonation of dodecane' with sulfuryl chloride, withchlorosulfonic acid, or with chlorine and sulfur dioxide. Instead ofutilizing the poly-(oxyethylene) glycols, in the esterificationreaction, ethylene glycol may itself be initially reacted to form thecorresponding ester of the monomer glycol in which the wife group of thesulfonic acid or the sulfonyl chloride esterifies one of the glycolhydroxyl groups, and thereafter reacting the w-hydroxy ester withethylene oxide or an ethylene halohydrin at condensation reactionconditions and for a reaction period of suflicient duration toincorporate the desired number of oxyethylene units into the molecule ofthe resulting sulfonic acid ester.

Other poly-(oxyalkylene) glycols, such poly-(oxypropylene) glycol,a,-hydroxypropyl-w-hydroxypropoxy-poly- (oxypropyleue), the polybutyleneglycols, a-hydroxybutyl-w-hydroxybutoxy-poly-(oxybutylene), and thepolyamylene glycois, a-hydroxyamyl-w-hydroxypentoxy-poly- (oxyarnylene),or the C C and/ or C alkylene oxides, such as propylene oxide, butyleneoxide, or amylene oxide may also be utilized in the reaction to form thecorresponding esters containing an average of from 2 to about 25oxyalkylene units per molecule. Similarly, in place of thepoly-(oxyalkylene) glycols, the corresponding halohydrins, such as thea-bromoand ot-chlorohydrin derivatives of the glycols may be utilized inthe condensation reaction with the sulfonyl chloride or sulfOnic'acidintermediates. In accordance with still another method of preparation,the sodium salt of dodecyl sulfonic acid may be reacted with anw-halogen-substituted alcohol to form thew-hydroxy-alkyl-dodecylsulfonate, which is thereafter condensed with analkyleneoxide, such as ethylene oxide to produce the hydrophilicpoly-oxyalkylene chain. In general, in reactions utilizing an alkyleneoxide or an alkylene halohydrin, the intermediate sulfonyl halide orsulfonic acid derivative of the hydrophobic hydrocarbon must beinitially reacted with a mono-glycol in order to provide a chain starterhaving a terminal hydroxyl group, although the sulfonic acid itself maybe used directly.

A more Water-soluble compound and one containing a more hydrophilicradical in the structure may be produced by sulfating the terminalhydroxyl group of the poly-(oxyalkylene) chain, thereby producing acompound of the following structure, in the case of thedodecylpolyoxyethylene) -sul-fonate derivative:

12 25-" 2( H ,,OSO M [w-Sulfato-poly oxyethylene) ]-dodecylsulfone wheren is a whole number having a value. of from 1 to about 25, M is hydrogenor an electropositive metallic radical, such as sodium, potassium,ammonium, etc.

A particularly preferred product of the type characterized as apoly-(oxyalkylene) glycol condensation product of. the hydrocarbonsulfonic acid isrepresented by the following structural formula:

S 01(0C ,Hm ,-OH An [w-hydr oxy-p oly (oxyalkylene) ]-alky1arylsulfonewhere m and n are whole numbers, n having a value of from 1 to 5, m avalue of from 5 to about 18 and x is a number selected from O, 1, and 2,provided xn+m l1, p is 2 or 3, and y has a value between 1 and about 25.

Another product of this invention, containing a different hydrophilicgroup, has the following structural formula, in which a long-chain alkylgroup (undecyl, in the formula illustrated) represents a typicalhydrophobic hydrocarbon group which may be substituted on the sulfonoradical present in the molecular structure of the product:

where n is a whole number having a value of from 1 to about 10 and M isselected from hydrogen and the electropositive metallic ions. Ingeneral, compounds of the above structure may be prepared by reacting asulfonated C parafiin (undecyl sulfonic acid) at esterifying reactionconditions with an w-hydroxy aliphatic acid and thereafter neutralizingthe resulting acid with a base to form the carboxylated salt, ifdesired. In an alternative procedure the sodium salt of undecyl sulfonicacid may be condensed with a halogen-substitued aliphatic acid(particularly a bromo or chloro-substituted aliphatic acid), and theresulting carboxylic acid condensation product neutralized, if desiredto form the corresponding carboxylate salt. Other methods ofsynthesizing compound of this type may be readily adapted to theproduction of the present compositions, methods which are apparent tochemists skilled in the art.

Still another structural variation of the present surface active agentscontaining a different water-solubilizing hydrophilic group is the typerepresented by the following structural formula:

Gm 2m+l Metal (sulfo-alkoxy)-alkylnaphthalylsulfone where n and m arewhole numbers, n having a value of from 1 to 3, m having a value of from5 to 9, x is a whole number having a value of from O to 2, y is a Wholenumher having a value of from 1. to 9 and M is selected from the groupconsisting of hydrogen and an electro positive ammonium or metallicradical. These compounds may be conveniently prepared by sulfonating analkyl naphthalene hydrocarbon, neutralizing the resulting sulfonic acidwith a base such as sodium hydroxide to form the sulfonate salt andthereafter reacting the sulfonate salt with a chloro orbromo-substituted sulfoalkane (a sulfonated chloroparaflin) in acondensation type reaction to form the above-indicated class of surfaceactive products and the halide salt of the base metal ion. In place ofthe chloroor bromo-substituted alkane reactant condensed with the sodiumhydrocarbon sulfonate derivative, a nuclearly sulfonated aromatichalide, such as p-bromophenyl sulfonate, may be utilized in the reactionto form a derivative having the following structure (which may also beformed by sulfonation of the reac 7 tion product of a phenolate and analkane sulfonyl halide):

R S 02M Hen-SOzO-Q Rn Hydrocarbon- (X-sulfophenoxy) -sulfone sodiumalkyl sulfonate salt) a product of the type represented :by thefollowing formula is formed:

HOIb-SOa-O-(C-Jim) 303M Hydrocarbon- (X-sulfo-X'-a1kylphenylalkoxy)-sulfne where Hcn, R, R and M are as indicated in the next precedingformula above, and m is a Whole number having a value of from 1 to about5.

In certain members of the general class of compounds herein provided amonoor poly-alkanolamine has sufiicient hydrophilic activity in solutionto provide a surface active compound when joined through an organicradical to a sulfo group bearing a hydrophobic hydrocarbon radical. Thesurface active members of this group have hydrocarbon radicalscontaining a relatively small number of carbon atoms, generally an alkylgroup containing fewer than about carbon atoms per hydrocarbon radical,a nuclearly alkyl-substituted aromatic hydrocarbon containing not morethan about 12 carbon atoms per alkyl substituent or a nuclearlyalkyl-substituted dinuclear aromatic hydrocarbon radical in which thealkyl group contain up to about 9 carbon atoms. Typical compounds ofthis general class are illustrated as follows:

0 H2 0 Hz 0 H Diethanolaminoethoxy-alkylphenyl-snlfone where n, m, and xare whole numbers, n having a value of from 1 to 3, m having a value offrom 5 to about 12, and x being 0, 1 or 2.

Cali 2+1 Diethanolaminoethoxy-alkylnaphthaIyl-sulfone CHzCHzOH CHaCHiOHwhere n, m and x are whole numbers, n having a value of 1 to 3, m avalue of from 3 to 9, and x a value of 0, 1 or 2.

OH: on, I daemon CnHa1SOr-O$HCH2 Dlpropanolaminopropoxy-octadecylsulfonefonyl chloride derivative of a hydrocarbon having a hydrophobichydrocarbon radical attached to the sulfo group thereof at reactionconditions which effect the condensation of one of the hydroxyl groupsof the alkanol amine with the sulfo groups of the sulfonic acid.

The resulting amine derivative may be made more soluble in water byreacting the sulfo-ester formed in accordance with the precedingcondensation reaction with a mineral or organic acid of sufiicientacidity to form the ammonium salt derivative of the condensationproduct, such as the product of the following structure formed byreacting nonylbenzene with chlorosulfonic acid to formnonylphenylsulfonyl chloride, thereafter reacting the resulting sulfonylchloride derivative with triethanolamine and forming the hydrochloridesalt of the resulting amine by adding sufficient hydrogen chloride orhydrochloric acid to the amine to convert the latter to the ammoniumsalt thereof:

[B- (Di-hydroxyethyl) -amino-ethoxy]-nonylphenyl-sulone hydrochloride Asurface active product having detergent properties, particularly inaqueous solution, and having more than one substituent or group ofsubstituents possessing hydrophilic properties is represented, forexample, in the composition of the following structure:

Dodecylphenyl-triethanolammonium sulfato-poly(oxypropy1ene)-su1fonatewhere n is a whole number having a value from 1 to about 50, preferablyfrom 2 to about 10. In place of the dodecylphenyl hydrophobic groupillustrated in the formula, other hydrocarbon groups such as alkyl,other aryl (such as naphthalyl and adiphenyl) and other aralkyl radicalsof the type shown in Table I above, may be substituted in the structureof the compound. Instead of the hydrophilic poly-(oxypropylene) group inthe above compounds, poly- (oxyethylene), poly-(oxybutylene) andpoly-(oxyamylene) radicals may be introduced into the structure of theproduct. In order to produce a product having optimum surface activitythe number of poly-(oxypropylene) groups or other poly-(oxyalkylene)radicals in the hydrophilic chain is adjusted to provide a product inwhich the hydrophilic eifect of the poly-(oxyalkylene) group issubstantial- 1 ly balanced with respect to the efiect of the hydrophobicgroup. Furthermore, a mixed or heterogeneous polyoxyalkylene'chain, suchas poly (oXyethylene)-poly (oxybw tylene) may be incorporated into thestructure of the hydrophilic portion of the molecule in place of ahomogeneous poly (oxypolypropylene) chain. Compounds of this type may beprepared by reacting dodecylbenzene with chlorosulfonic acid atconditions whereby the corresponding dodecylphenyl-sulfonyl chloride isformed, thereafter reacting the sulfonyl chloride derivative withpolypropylcne glycol (or other polyalkylene glycol, either homogeneousor of the mixed type), sulfating the terminal hydroxyl group of thepolyalkylene glycol monoester with concentrated sulfuric acid oleum orsulfur trioxide to form a terminal sulfate ester group, and reacting thesulfate ester with triethauolamine (or with any other basic nitrogencompound, such as ammonium hydroxide, other ethanolarnines orpropanolamines, pyridine, etc.) to form the desired ammonium orsubstituted ammonium hydroxide product. i a

, The hydrophilic substituent in-theabove series of com pounds, when asulfonic acid or sulfate ester group, may generally be introduced intothe structure of the compound either by reacting the previously formecldetergent base with concentrated sulfuric acid, oleum or sulfurtrioXide, or if the detergent is unstable in the presence of the latterreagents, by reacting a sulfonylchloride derivative of the detergentbase, such' as the sulfonyl chloride derivative of the hydrophobichydrocarbon radical with the sodium salt of the organic radical bearingthe hydrophilic group. In those instances in which a poly-(oxyalkylene)group is introduced into: the structure of'the compound, a sulfonylchloridederivative of the hydrophobic hydrocarbon group of thehydroxy-substituted derivative thereof is condensed with the appropriatepolyal'kylene glycol, or the sulfonic acid with the'alkylene oxide, inthe presence of catalytic amounts of a suitable base such as sodiumhydroxide (dry, powdered or a caustic solution of the base), sodiumacetate, pyridine, or other'basic tertiary amine, continuing thereaction untilthe desired number of alkylene oxide units has beenintroduced into the poly-(oxyalkylene) chain. Suitable techniques andprocesses for this purpose are well known in the. chemical arts withoutspecific reference herein to processes available for this purpose.

For those compounds of the present invention which have surface activityand particularly the compounds which possess detergencyin aqueous andnonaqueous solvents, the hydrophobic hydrocarbons in general balance theeifect of the hydrophilic substituent when the product is dissolved in asuitable solvent therefor. The structure of the hydrocarbon portion ofthe molecule, in general, determines the surface activity, thesolubility of the compound in particular solvents such as water, itsmelting point or softening point and many other physical properties ofthe compound when utilized as a detergent. The hydrocarbon portion ofthe molecule may be an aliphatic alkyl group containing at least 8'carbon atoms per group or a cyclic hydrocarbon group containing an alkylsubstituent on one of the nuclear portions of the cyclic hydrocarbonring, the products possessing. surface activity containing at least 11carbon atoms per group in the alkyl-substituted cyclic hydrocarbonportion of the molecule. When alkyl, the hydrocarbon radical may bederived from suitable petroleum fractions containing hydrocarbons of thedesired chain length and these may be separated from strai ht runpetroleum distillates, in the case of the aliphatic alkanes, or from theconversion products of petroleum hydrocarbon cracking reactions,olefinic hydrocarbon polymerization reactions, and alkylation reactionsof suitable source, depending upon the molecular Weight and structure ofthe hydrocarbon desired. Thus, in the preparation of a dodecyl sulfonicacid starting material, the tetramer fraction of a propylenepolymerization product or its hydrogenated analog may be separated fromthe total polymeric product of a propylene polymerization process andthereafter subjected to sulfonation to form the corresponding sulfonicacid derivative. Another typical source of such aliphatic hydrocarbonscontaining at least 8 carbon atoms per molecule is the dehydrationproduct ofan aliphatic alcohol containing the same number of carbonatoms, the olefinic product of which may be subsequently hydrogenated toit) form the corresponding. aliphatic alkane. Thus, lauryl alcohol(dodecanol) may be dehydrated by passing'the alcohol over activatedalumina to'form dodecylene and the latter product may be hydrogenated bypassage of the dodecylene with hydrogen. over a nickel hydrogenationcatalyst to form dodecane. When the hydrophobic hydrocarbon portion ofthe molecule is a hydroaryl or naphthenyl group, the aryl hydrocarboncontaining a corresponding number of carbon atoms may be hydrogenated tosaturate the hydrocarbon nucleus, or the hydrocarbon may be separated,as a naphthene from a straight run hydrocarbon distillate containing theappropriate naphthene desired. Thus, an alkyl cyclohexane may be formedby hydrogenating the corresponding alkyl benzene or it may be separatedfrom certain straight run petroleum fractions containing alkylnaphthenehydrocarbons. When the cyclic hydrocarbon portion of the molecule isaryl, allryiaryl, arallryl or a partially hydrogenated analog of thesearyl hydrocarbons, the starting material may be separated from theappropriately boiling petroleum distillates containing the same or fromthe conversion prod nets of petroleum fractions, such asa catalyticallycracked gas oil fraction, one of the common sources of benzene, toluene,the xylenes or other desired alkyl aromatic hydrocarbon.

The hydrocarbon starting materials herein characterized as alkylaromatic hydrocarbons or hydroalkylaryl hydrocarbons, in which the alkylgroup contains at least 5, up to about 20 carbon atoms per group, forthe production of specific types of surface active agents, generallymust be prepared in a preliminary stage of the process by all-:ylationof the corresponding cyclic hydrocarbon nucleus. Thus, benzene, toluene,Xylene, ethylbenzene, cumene, butylbenzene, naphthalene,methylnaphthalene, diphenyl, etc. may be a lrylatcd with an olefinichydrocarbon containing the number of carbon atoms desired in thelong-chain alkyl substituent attached to the aromatic nucleus, or withan alcohol or alkyl halide having the desired number of carbon atoms, inthe presence of an acid-acting alkylation catalyst to promote thecondensation of the aromatic hydrocarbon and the desired alkylatingagent. Thus, benzene may be alkylated with dodecylene (such as apropylene tetramer fraction) in the presence of an alkylation catalyst,such as liquid anhydrous hydrogen fluoride, concentrated sulfuric acid,aluminum chloride, etc. to form dodecyl-benzene which is subsequentlyutilized as the charging stock in the formation of the presentsulfo-ester product as hereinabove indicated. In the production of thosecompounds herein characterized as alkyl naphthenes or partiallyhydrogenated alkylaryl hydrocarbons, the alkylated aromatic hydrocarbonmay be subjected to partial or complete hydrogenation in the presence ofhydrogen and a hydrogenation catalyst such as nickel supported onkieselguhr at such conditions of hydrogenation as to yield the desiredpartially or completely hydrogenated alkyl aromatic hydrocarbon.

The sulfonic acid derivative of the hydrocarbon utilized in the presentprocess may be prepared by sulfonating the aliphatic alkane, the alkylaromatic or alkyl hydroarornatic hydrocarbon corresponding in structureto the hydrocarbon portion of the product ultimately desired as thesurface active agent of the present invention. Suitable sulfonatingagents for this purpose include, concentrated sulfuric acid containingat least 95% sulfuric acid by weight, sulfuric acid oleums which containfree sulfur trioXide dissolved in sulfuric acid, chlorosulfonic acid, orsulfur trioxide itself in one of its allotropic alpha, beta, orgamma-forms. These form the sulfonic acid or chlorosulfonic acidderivative, which may be hydrolyzed with water to yield thecorresponding sulfonic acid product or used directly. The proceduresutilizable for sulfonation are generally well known in the art and mayalso be utilized for sulfonation of the alkane, alkylaryl chloride byreaction with thionyl chloride, phosphorus I trichloride or pentachloride, or the like.

The sulfo-ester products herein provided may be composited with otherorganic or inorganic materials to provide surface active or detergentcompositions when the I sulfo-ester product is a compound having surfaceactivity or detergency. Thus, the sulfo-ester may be suitably compositedwith a builder salt or water-softening component such as sodium sulfate,sodium carbonate, ammonium sulfate, an inorganic phosphate orpolyphosphate salt, such as an alkali metal or ammonium pyrophosphate,tripolyphosphate, hexametaphosphate, or other polyphosphate salt, sodiumsilicate, calcium or magnesium chloride, etc. or with a water-solublecellulose derivative, such as sodium carboxy methylcellulose, or withother material which has a specific action when composited with adetergent or surface active agent.

The present invention is further illustrated with respect to several ofits specific embodiments in the following examples, which, however, arenot intended to restrict the generally broad scope of the inventionnecessarily in accordance therewith.

Example I A compound having surface active properties in aqueoussolution and having the following structural formula: C H -SO -OC H SONa [dodecyl-(sodium sulfoethoxy)-sulfone] is prepared by reacting sulfurdioxide and chlorine With dodecane to form the correspondingdodecylsulfonyl chloride, thereafter reacting the resulting product withethylenechlorohydrin to form dodecyl-(Z-chloroethoxy)-sulfone, andcondensing the latter intermediate with sodium sulfite to form thecorresponding sodium sulfonatc derivative. In this process dodecane (thehydrogenated alumina-dehydration product of lauryl alcohol or thehydrogenated C propylene tertramer fraction, boiling from 170 to about225 C.) is reacted with one-third of an equivalent of chlorine in thepresence of excess sulfur dioxide at a temperature of 2535 C.,

underillumination of light having considerable intensity in the range30005000 A., the reaction mixture being stirred during the addition ofthe gaseous reactants to the dodecane. The sulfonyl chloride isseparated by distillation from unreacted dodecane and by-products, andis reacted with a molar equivalent of ethylenechlorohydrin in thepresence of an excess of aqueous sodium carbonate at a temperature of 50C. The organic portion of the product is extracted from the reactionmixture with diethyl ether and the chloroethyl-dodecylsulfonatecomponent of the extract, after evaporation of the ether, reacted withanhydrous sodium sulfite at a temperature of 100 C. to introduce thesodium sulfonate group on the ethoxy radical of the product. The productis water-soluble and the desired dodecyl-(sodium-ethoxy)-s11lfone isrecovered from admixture with sodium chloride in a substantially purestate by extraction of the dried residue recovered by evaporation of theaqueous solution to dryness with 95% ethanol. The over-all yield of theproduct is 82% of theoretical, based upon the quantity of dodecanestarting material. The product, when dissolved in water to the extent of0.3% by weight, provides an aqueous detergent solution having adetergency substantially greater than a solution of laurylsulfate of thecorresponding concentration of detergent therein.

.Example II V A'detergent having the following structural formula:

" on, I

Sodium dodecyltolyl [polyoxyethylene-w-sulfatol-sulfone is prepared bysubjecting a dodecyl-toluene alkylate hydrocarbon to chlorosulfonationto form the corresponding dodecyl-tolyl sulfonyl chloride, reacting thelatter with ethylene glycol, condensing the resulting glycol sulfo-csterwith ethylene oxide to introduce a poly-(oxyethylene) chain into thestructure of the compound, sulfating the terminal hydroxyl group at theend of the poly-(oxyethylene) chain to form the acid sulfate ester, andneutralizing with sodium hydroxide to form the sulfate ester product.

For the above series of reactions, dodecyltoluene is reacted with 1.2molecular equivalents of chlorosulfonic acid at 40 C. and at atmosphericpressure for 3 hours, the sulfonyl chloride is separated by vacuumdistillation, and thereafter molar excess (6 mols) of ethylene glycol isadded to the sulfonyl chloride to effect the mono-esterificationreaction. The resulting ester containing a free terminal hydroxyl groupafter being separated from the excess glycol, is reacted with ethyleneoxide to introduce a hydrophilic poly-(oxyethylene) chain into thestructure of the compound. For this purpose, about 12-14 molarproportions of liquid ethylene oxide per mole of the preparedglycol-sulfo-ester and about 2 weight percent of powdered sodiumhydroxide are introduced into a rotating pressure autoclave, theautoclave sealed, pres sured with nitrogen to a gage pressure of 200-lbs/in. and heated to a temperature of 100 C. for 2 hours as theautoclave is slowly rotated, during which time the ethylene oxide reactscompletely. The product of the reaction is removed from the autoclave,and the poly- (oxyethylene) condensation product of theglycol-sulfoester recovered in a yield of approximately 87% oftheoretical, based upon the initial charge of dodecyltoluene. Theproduct is a waxy solid and is readily dissolved in both hot and coldwater. When tested for its detergency in accordance with standardprocedures therefor, utilizing a Launder-O-Meter, the product has adetergency somewhat greater than a sodium sulfate builtalkylarylsulfonate (dodecylbenzene sulfonate) detergent.

The above product may be converted to a solid saltlike material ofsubstantially greater solubility in water by converting the aboveproduct to its sodium sulfate derivative. In the latter conversion, theethylene oxide condensation product of the dodecyltolyl-hydroxyethylsulfonate, as prepared above, is sulfated with concentrated (98.5%)sulfuric acid at a temperature of 40 C., utilizing 5 molar proportionsof acid per mole of condensation product, which is added to the lattergradually, and with stirring over a period of 2 hours, cooling, ifnecessary, to maintain the temperature at approximately 40 C. Thereaction mixture when neutralized with sodium hydroxide, evaporated todryness and extracted with ethanol to separate the organic product fromthe sodium sulfate by-product has substantially the same detersiveefliciency at optimum concentrations as the unsulfated sulfo-ester andmuch greater solubility in both hot and cold water.

In the preparation of the unsulfated intermediate detergent product,greater or lesser amounts of ethylene oxide may be introduced into thecondensation reaction mixture to produce products having correspondinglylonger or shorter poly-(oxyethylene) chain lengths. The products thusproduced vary in their water solubility in direct proportion to thenumber of oxyethylene units per chain.

In general, the greatest detergency for the dodecyltolyl sulfo-esters ofw-sodium sulfate-poly-(oxyethylene)-etha i3 nol are those members of theseries containing. from to about 20, preferably from 12 to 16,oxyethylene units per molecule.

Example III A surface active agent having the following structuralformula:

CHz-SO:OCH2COON3 Nonylbenzyl-sodium carboxymethoxy-sulfone is preparedby chloromethylating nonylbenzene, reacting the resultingnonylbenzylchloride with sodium sulfite to form the corresponding sodiumnonylbenzyl sulfonate and thereafter reacting the latter salt withsodium chloroacetate to form the surface active product hereinabovedesignated.

Chloromethylation of nonylbenzene is efiected in the presence of a mildPriedel-Crafts catalyst by reaction of chloromethyl ether underconditions whereby a single chloromethyl group is substituted on thearyl nucleus. In order to prevent polychloromethylation a molar excessof nonylbenzene is utilized in the reaction. Ten moles of nonylbenzene,two volumes of carbon disulfide and five moles of chloromethyl ether ina stirred flask, and 25 weight percent of anhydrous stannic chloride(based on the ethers) are added dropwise, while cooling to maintain atemperature of 15-20 C. After all of the catalyst has been added, themixtureis stirred for an additional hour, then poured onto ice, theorganic layer separated, washed, and distilled to recover the desirednonylbenzylchloride. A yield of 60% of theoretical, based on thequantity of chloromethyl ether charged, is recovered (B. P. 125-127 n=l.515O, chlorine content: 13.4% found, calculated 13.3%).

The nonylbenzylchloride is thereafter mixed with a molar excess ofsodium sulfite in concentrated aqueous solution and the mixture heatedto a temperature of 120 C. in a stirred autoclave for 3 hours, withstirring, to form the nonylbenzylsodium sulfonate derivative, utilizedin the following reactions.

The sulfonate product prepared as indicated above is thereafter mixedwith a molar excess (1.5 moles per mole of sulfonate) of anhydrous,finely powdered, sodium chloroacetate and heated to a temperature of 150C. with stirring for a period of 1.5 hours. The resulting reactionmixture is cooled, and thereafter extracted with anhydrous methanol torecover the desired organic detergent salt from the inorganic componentsof the reaction mixture. The alcohol extract solution, when evaporatedto dryness, yielded the surface active product hereinabove indicated,that is, the sodium salt of nonylbenzylcarboxymethoxysulfone. Whentested for its detergency in soft water, its effectiveness for thispurpose is approximately as great as that of the sodium salt of oleicacid.

Certain alkylphenyl-mono-chloroalkanes may be prepared by alkylation ofthe appropriate phenyl-alkylhalides containing from 1 to 5 carbon atomsin the alkyl group of the phenylalkylhalide. The sulfonates derived fromthese may be condensed with other halo-aliphatic acids to provide aseries of products having surface activity, although the acetic'acidderivatives are, in general, preferred in this synthesis.

Example IV A product having surface activity in both aqueous andnon-aqueous solvents, and referred to as:w-(N-diethanolamino)-ethoxy-dodecylsulfone having the followingstructure:

is prepared by reacting dodecane (hydrogenated propylene tetramerfraction) with sulfur dioxide and chlorine and reacting the product withtri-ethanolamine in the presence of aqueous sodium carbonate. In thisreaction, dodecane is sulfochlorinated in the manner described inExample I, and the recovered. reaction product is mixed with a molarequivalent of tri-ethanolamine dissolved in dilute aqueous sodiumcarbonate solution. The reaction is continued until allof the sulfonylchloride is esterified with alcoholic hydroxyl groups, the product beingthen recovered from the aqueous solution by extraction with diethylether and subsequent removal of the diethyl ether.

This product is a soft, waxy, semi-solid material, soluble in water andliquid hydrocarbons, as well as alcohols, ethers, ketones, etc., whichsolutions exhibit surface active properties. A 0.3% aqueous solution ofthe product, when tested in a Launder-O-Meter, utilizing the standarddetergent test procedure, for example, exhibits approximately the samedetergency as an aqueous solution of sodium sulfate-built sodiumdodecylbenzene sulfonate C2H40)8HOH Dodecyl- [N-di- (w-hydroxy-poly-oxyethylene] -amino-ethoxysulfone In the preparation of thisproduct, one molar proportion of thew-(N-diethanolamino)-ethoxy-dodecylsulfone, prepared as indicated above,is mixed with approximately 14-22 molar proportions of ethylene oxideand about 2 weight percent of sodium acetate in a rotating pressureautoclave, the ethylene oxide being charged into the autoclave as aliquid. The pressure within the autoclave is increased to 150 lbs/in.with compressed nitrogen and the autoclave heated to a temperature of C.as the reaction mixture is stirred by rotation of the autoclave. After 3hours, the product of the reaction is allowed to solidify by cooling toroom temperature. The product is a hard, waxy solid, very soluble inwater and slightly soluble in pentane or benzene.

The detergency of the product, as determined by a Launder-O-Meter testprocedure is approximately 120% of the detergency of sodiumdodecylbenzene-sulfonate at equivalent concentration in aqueoussolution, as indicated by its ability to whiten soiled cotton muslin inthe deten gency test procedure.

I claim as my invention:

1. A compound selected from the group consisting of dodecyl-(sodiumsulfoethoxy)-sulfone, sodium dodecyltolyl-(polyoxyethylene-w-sulfato)sulfone containing an average of from about 13 to about 15 oxyethyleneunits in the polyoxyethylene radical, w-(N-diethanolamino)-- ethoxydodecylsulfone,dodecyl-[N-di-(w-hydroxy-polyoxyethylene)J-amino-ethoxysulfonecontaining an average of from about 8 to about 12 oxyethylene units perpolyoxyalkylene chain, and diethanol-aminoethoxy-dodecylphenylsulfone.

2. Dodecyl-(sodium sulfoethoxy)-sulfone.

3. Sodium dodecyltolyl-(polyoxyethylene w sulfate)- sulfone containingan average of from about 13 to about 15 oxyethylene units in thepolyoxyethylene radical.

4. w-(N-diethanolamino)-ethoxy dodecylsulfone.

5. Dodecyl [N di (w hydroxy-polyoxyethylene) amino-ethoxysulfonecontaining an average of from about 8 to about 12 oxyethylene units perpolyoxyalkylene chain.

6. Diethanol-aminoethoxy-dodecylphenyl-sulfone.

(References on following page) References Cited in the file of thispatent UNITED STATES PATENTS Schoeller et al., "Aug. 21, 1934 HoeifelmanJuly 23, 1940 5 Kritchevsky Oct. 28, 1941 Adams Dec. 16, 1941 OTHERREFERENCES McCutcheefi: Synthetic Detergents, 1950, pp.45 -6.

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF DODECYL-(SODIUMSULFOETHOXY)-SULFONE, SODIUM DODECYLTOLYL-(POLYOXYETHYLENE-W-SULFATO) -SULFONE CONTAINING AN AVERAGE OF FROM ABOUT 13 TO ABOUT 15 OXYETHYLENEUNITS IN THE POLYOXYETHYLENE RADICAL, W-(N-DIETHANOLAMINO)ETHOXY -DODECYLSULFONE,DODECYL-(N-DI-(W-HYDROXY-POLYOXYETHYLENE,)-AMINO-ETHOXYSULFONECONTAINING AN AVERAGE OF FROM ABOUT 8 TO ABOUT 12 OXYETHYLENE UNITS PERPOLYOXYALKYLENE CHAIN, AND DIETHANOL-AMINOETHOXY-DODECYLPHENYLSULFONE.